Water soluble cellulose ethers



, products as are UNI-TED STATE 2,160,782 wa'raa sowsnu csnwnosn n'rnuns -Albert'l..

TheDow Maasbers, Midland,

a corporation of Michigan Serial No.

scams. "(01. 260-231) This invention relates to a method'for the preparation of water-soluble cellulose ethers and more particularly water-soluble ethyl and methyl celhilose. 1

It has been known for many years that certain of the mono-alkyl ethersof cellulose are soluble in or are swelled by, cold water. Such ethers have been reported variously as containing from 16 130i percent methoxyl in the case of methyl cellu- 10 lose and correspondingly from about 25 to 33 per cent ethoxyl in the case as ethyl cellulose. In either instance the degree of substitution reported in the prior art has been equivalent to from about 1 to about 1% or slightly more alkoxyl groups per anhydro glucose-unit. In the ordinary procedure for preparing a water-soluble,

lower alkyl ether of cellulose, considerable diiliculty has been experienced in isolating the cellulose ether from the-reaction medium, and such obtained have been found to be somewhat colored, both in the dry form and in water solution. Many of the water-soluble lower alkyl ethers of cellulose heretofore prepared retain considerable 'amounts of inorganic matter, 25 especially the salt which occurs as a by-product of the etherifying reaction. Owing in part to the diillculty of completely separating the ether from the reaction mixture. the yields in the prior art processes are generally low. The principal 0 disadvantage inherent in the old processes is that they do not produce uniformly etherified' products, hence the products obtained are not uniformly soluble.

It is, accordingly, among the objects of the 35 present invention to provide a' process whereby a water-soluble, lower alkyl ether of cellulose may be prepared which isunitormly soluble in cold water, which is low in ash and salt content, and which possesses a good white color. It is another 40 object to provide a process whereby such ethers .may be obtained in good yieldsand easily isolated from the reaction mixture. It is a further object of the invention to provide a process whereby a water-soluble methyl cellulose may be prepared having the aforesaid desired characteristics and in good yield. I have now found that the foregoing objects may be attained by the use of an alkali cellulose of certain characteristics, and controlling the conditions of etheriflcation and isolation of the product. The cellulose ethers made according to my present invention are soluble. in cold water. 7 form gels when a water solution is heated, precipitate as disperse particles in boiling water. and 5 are obt ned ingood yields. The degree of sublose ethers are requirements stitution in the I have obtained alkoxyl regardless is methoxyl or ethoxyl. number of substltuent groups, ethyl cellulose made according from about 1 to vention contains roups per unit,

tains from about 1.

cellulose un is from about 25 t Mich. assignor to ChemicafCompany, Midland, Mich.,

No Drawing. Application August 8, 1938,

5 PATENT" orgies it in the ethers which 0 33 per cent of whether the alkoxyl group the per unit. My invention resides inthat cellulose ethers having the aforesaid desired characteristics can alkali cellulose containing at not substantially ove of c droxide per part least 0.9 part, but no parts, of water per part 0 to my process,

be produced by least Expressed in terms of the water-soluble to the present inabout 1.5 ethoxyl while the methyl cellulose con- 5 to about 2 methoxyl groups the discovery employing an 0.9 part, but

rv 1.2 parts, of sodium hyellulose,- and containing at V t substantially more than 1.5

fcellulose.

an alkali cellulose' having the According above-defined alkali to cellulose and water to cellulose ratios is caused to react wlth an alkylat- '20 halide" or a lower ing agent such as alkyl sulphate, and especially with ride, methyl'bromide, (methyl .ride, ethylbromide, or dium hydroxide content of the substantially comp Y tion with the said alkyl I have found that if a. ratio may be employ content of the ether produc solubility in water 'the alkali to cellulose r iodide, ethyl iodide, until the soalkali cellulose is letely neutralized by interacating agent.

lower alkali to cellulose ed than 0.9:1,

ed will be low,

methyl chloethyl chlothe alkoxyl and its will be non-uniform. When, however, an alkali cellulose is employed wherein atio varies between the rather closely defined limits of 0.9:1 to 1.211, the

ether products obtained or ethyl halide are containing from 25 to 33 per cent by reacting with a methyl found to be ethers of cellulose alk'oxyl groups,

and having uniformly good solubility in cold water.

below about 25 C.

45-50 C. withouttion.

For purposes the term cold water w note waterbelow ordinary room dissolved in cold tion may be employed at tem of the present description,

ill be employed todesigtemperature, 1. e.

Once the water-soluble celluwater, the soluperatures up to material gelatlon or precipita- The alkali cellulose conforming be prepared by of cellulose, alkali, portion oriit may tween about to the above and water in the proper probe prepared by havinga hydroxide. The cellulose aggregate immersing a te in a bath of liquidsodium concentration of be- 5' I;2' 'per cent sodium should be re-' as,to alkali and water content may grinding or macerating a mixture moved from the alkali bath as soon as it has absorbed from 1.8 to 2.7 times its weight of alkali solution, depending on the concentration of said solution, as shown by the following table.

/ Weight. of alkali solution or unit weight of cellucse to give desired alkali and water to cellulose Concentration of alkali solution, pcrratios in the alkali mum cent lose Minimum Maximum m r-repr s s a s sa 's s s s s s s m b- O! Gibb o'e'6%8=e which are non-uniform as to their water solulent to the amount of alkali present in the alkaliand preferably at about 70 in the range from about 90 to about 120 C. are

halide has. reacted of this metto effect the shredder. To the between 85 bility.

In the etherification reaction, the amount of alkyl halide employed should be at least equiva:

cellulose. It is preferable that the reaction be discontinued shortly before the alkali present is completely neutralized, i. e. while some alkali and some alkyl halide remain unreacted'. This procedure permits isolation of'the celluloseether from an alkaline medium and avoids acid'hy- Y drolysis and degradation of the ether which may occur when the alkali is completely, neutralized during etherification in the presence of excess etherifying agent. The temperature of .etheriflcation will vary dependi'ng'upon the alkyl halide employed and the ease with which the alkyl'hal-' ide reacts with alkali cellulose. In the case of methyl chloride, the etherification may be carried out in the range from 50-l00 0., whereas in the case of ethyl chloride, higher temperatures, i. e.,

preferred. After the alkyl with nearly all of the alkali present in the alkali cellulose, the reaction vessel is cooled ,to stop the reaction and the crude alkyl. cellulose is'removed from the still slightly alkaline medium for purification. The product of reaction is characterized by its solubility in cold water and its insolubility in hot water; Advantage is taken purification by washing the product, with water at a temperature.above about 60 0., and preferably at a temperature and 100 C.,-to remove salts and to eflect volatilization of any remaining alkyl halide or of any methyl or ethyl alcohol or ether formed as by-products during the reaction..

The following example illustrates thepractice I of my invention: 1.25 pounds of purified wood pulp was shredded until fi'ufly in a Baker-Perkins shredded cellulose was added 2.5 pounds of 50 per cent sodium hydroxide solu- .tion.

0., or higher,

Shredding was continued at 60 C. for 20 minutes while the cellulose absorbed the alkali solution. The alkali cellulose was cooled to about room temperature and 3.5 pounds of the material was placed in a pressure vessel to which methyl chloride was added from a cylinder until the internal pressure on the reaction vessel was pounds sense, or about 90 pounds absolute, per.

' Heating was continued for 12.5 hours at 70 C.

and a total of 1.5 pounds of methyl chloride was supplied to the reaction vessel, although only a. little over 1 pound reacted. At the end of this period, the reactor was cooled,-the remaining methyl chloride was vented to a recovery system,

and the reaction mixture containing crude methyl cellulose was removed from the pressure vessel. Nearly all of the alkali present was neutralized during the "reaction, only 0.6 per cent of the weight of methyl chloride-free reaction mixture being sodium hydroxide. The methyl cellulose was washed with hot distilled water in a baskettype centrifuge until free of sodium hydroxide and salt. The temperature of the water used for washing the product was from to C. A methyl cellulose yield of,about per cent was obtained, based on the cellulose employed.

A 5 percent solution of the so-formed methyl cellulose in distilled water at 20 C. had a viscosity of 59 seconds as measured in a standard,

bubble viscometer, the tubes of which have an internal diameter of 1.5 centimeters and a total length of 70 centimeters with the graiiuations 50 centimeters apart. The length of the bubble in the tube was 4 centimeters. The methyl cellulose had an ash content of 0.12 per cent and a methoxy] content of 29.0 per cent. When cc. of a 1 per cent solution of the methyl cellulose in cold water (5 C.) was centrifuged in a graduated tube at 2000 R. P. M. for 15 minutes, only a minute trace-ofa watery-gel was thrown to the bottom of the tube.

The water-soluble methyl cellulose prepared as described in the above example had an unusually 10w ash content and high uniform solubility in cold water when compared with methyl cellulose as ordinarily obtainable from tofore-described processesthe here The properties of three different viscosity I of methyl celluose prepared according to the present invention were compared with correspondmg viscosity types of two other samples of commercially available water-soluble methyl cellulose. The compound prepared according to the present invention is designated in the following table as A, while the commercial samples are des ignated as B and C, respectively. 7

- Viseos-- 33 33 Percent Sample Viscosity type ity,se'ccmnbus meth- Color 7 ends on oxyl 12. 0 0. 9 v 31. 2 White 11.2 0.26 21. 7 YB.

23. 0 2. 54 10. 1 White 80 30.4 White 73 0.3 23.7 YB.

143 3.2 19.0 White 708 0. l7 25.0 White 421 0.44 24.0 YB. 283 2.76 17.2 White 'Y B-yellow-brown tinge.

From the stand p oint of color, the methyl cellulose prepared according to the present invention was equaltoor betterthan the color of .other commercially available samples. Samples A-and Binall these viscosity types were both characterized by solubility in cold water and insolubility in hot water. Sample B had an undesirable yellowish tinge both in the dry form and in water solution. Sample C was characterized by good solubility in cold water and 'fairly high solubility'in hot water. For this reason the ash content of the various C samples was considerably higher than the corresponding sample made according to the present invention, as the inorganic matter could not be removed by washing with hot water. Samples B and C were both characterized by lower alkoxyl content (16.l-24.9 per cent vs. -312 per cent) and by less uniform solubility than sample A. Thepresent invention then provides a uniformly 'cold-water -soluble cellulose ether which can be purified by the simple process of washing with hot water and which has'a low ashcontent and an excellent white color.

The actual temperature at which methyl cellulose, prepared according to the present irlvention, may be precipitated from aqueous-solution depends to a great extent upon the concentration of thesaid aqueous solution. The following table illustrates the gelation characteristics of a sample of low viscosity methyl cellulose which could be dissolved in-cold water I and'which would remain in solution 'therein at the water-soluble methyl or ethyl cellulose re:-

temperatures up to about C. without sign of precipitation.

Gelation and precipitation of methyl cellulose i from watersolution-weakening Temp. at 'lenlp. at

Temp. at

Concentration of aqueous which solid which ation is perse pre solution, percent first gel llgms, cipimte served, C. v forms, C.

No apparent gel or precipitate formed up to 100 0. Solutions became slightly cloudy at about 59-62 C.

' Methyrcellulose of the herein-described type I is useful for a variety of purposes. It' may be "printed .from cold water solutio'rronto' cloth, and-set bymeansof heat, to produce a damask eflect, or the so-treated cloth may be dyed and and about 100 C.

ALB

employed.

I therefore particularly point out,and distinctly claim as-my invention:

1. The process-which comprises reacting an alkali cellulose containing at least 0.9 and not substantially greater than,1.2 parts of sodium hydroxide and at least 0.9 and not substantially greater than 1.5 parts of water per part of cellulose, by weight, with an alkylating agent selected from the class consisting of the methyl The water-soluble I and ethyl halides and-sulphates, the alkylating agent being supplied in quantity at least equivalent to the sodium hydroxide present, continuing the reaction until the sodium hydroxide in the alkali cellulose is substantially completely neutralized, and discontinuingthe reaction while the reaction mixture is still slightly alkaline,

thereby toproduce a uniform cold-water-soluble,

lower alkyl ether of cellulose containing from about 25 to about 33 per cent alkoxyl groups, and characterized by solubility in water at temperatures below room temperature and insolubility in water at temperatures above C.

2. The process which comprises reacting an .alkali celluiose containing at least 0.9 and not substantially. greater than 1.2 parts of sodium hydroxide and at least 0.9 and not substantially greater than 1.5 parts of water per part of cellulose, by weight, with a methyl halide, the latter being supplied in quantity at least equivalent to the sodium hydroxide present, continuingthe reaction until the sodium hydroxide in .the alkali cellulose is substantially completely neutralized, and discontinuing the reaction while u the reaction mixture is still slightly alkaline,

thereby to produce a uniform cold-water-soluble about 33 per cent-methoxyl groups and characmethyl cellulose containing irom about 25 to terized by solubility in water "at temperatures below room temperature and insolubility in water at temperatures above 65 C.

3. The process according to claim '2, wherein the methyl halide is methyl chloride and the temperature of methylation is between about '55 ERT T. MAASBERGQ 

